CN101848946B - Gas-phase polymerization process - Google Patents

Gas-phase polymerization process Download PDF

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CN101848946B
CN101848946B CN200880113273XA CN200880113273A CN101848946B CN 101848946 B CN101848946 B CN 101848946B CN 200880113273X A CN200880113273X A CN 200880113273XA CN 200880113273 A CN200880113273 A CN 200880113273A CN 101848946 B CN101848946 B CN 101848946B
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fluidized
bed
gas
density
fluidizing medium
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CN101848946A (en
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平·W·蔡
罗杰·B·佩因特
简·W·范艾格蒙德
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WR Grace and Co
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Dow Global Technologies LLC
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Abstract

A process for polymerizing one or more olefins in a gas-phase polymerization reactor is provided. The gas-phase reactor has a fluidized bed and a fluidizing medium. The flidizing medium has an operating density and an operating velocity. The process includes determining a critical gas velocity and/or determining a critical gas velocity for the polymerization. The operating gas density and/or the operating gas velocity for the fluidizing medium is then adjusted to be less than or equal to its respective critical value. The process includes increasing the bulk density of the fluidized bed, The increase in the fluidized bed bulk density increases productivity without increasing reactor residence time.

Description

Gas phase polymerization process
The reference of related application
The application requires the U.S. Provisional Application No.60/957 of submission on August 24th, 2007, and 888 rights and interests are all introduced the application as a reference with it.
Background of invention
Present disclosure relates to the method for preparing polymkeric substance, and relates to especially the vapour phase polymerization of alkene.
Vapour phase polymerization is the currently known methods for the preparation of polymkeric substance.Vapour phase polymerization production efficiency is near the maximum value of production rate of polymer.Fixedly the time, the charging capacity (inventory) that increases reactor is to reach the maximized a kind of approach of producing when the volume of Gas-phase reactor.The reactor charging capacity can increase by improving fluidized-bed accumulation density (namely improving fluidisation tap density (fluidized bulk density)).
There is the uncertainty of height in the trial that operates the fluidisation tap density in order to increase productivity.The control of fluidisation tap density is complicated and difficult.There is complicated influencing each other between the tap density of fluidized-bed and many operating parameterss such as the upper limit/lower limit bed pressure/weight, bed height, bed tempertaure, gaseous tension, composition and flow velocity, particle rheology, bed deposition density (bed settled bulk density) and fluidized state.Be difficult to work out record all these parameters and the actually operating condition that calculates to a nicety under the fluidized-bed model of fluidisation tap density feature.This uncertainty causes the risk of (sheeting), one-tenth piece (chunking), fouling, bed collapse and/or reactor shutdowns in flakes.Realize that by controlling the fluidisation tap density the maximized advantage of polymer production is with respect to these risk evaluations.
Expectation be to improve the gas phase polymerization process that fluidized-bed is piled up density and avoided simultaneously in flakes, becomes piece, overheated, bed collapse and/or reactor shutdowns.
Summary of the invention
Present disclosure relates to for improving the gas-phase polymerization reactor fluidized-bed piles up method and the reactor of density.The application's method increases polymer production by improving fluidized-bed accumulation density.Fluidized-bed is piled up density when increasing, in flakes, become Risk Reduction or this risk of piece, overheated, bed collapse and/or reactor shutdowns not to exist.
In embodiment, provide the method that is used at one or more alkene of Gas-phase reactor polymerization.This Gas-phase reactor has fluidized-bed and fluidizing medium.This fluidizing medium has operating air density.The method comprises the critical gas density that is identified for fluidizing medium.Adopt following formula to determine critical gas density,
( a × APS × SBD SGV ) b
Wherein a is constant, and its value is approximately 3.5～approximately 6.2; B is constant, and its value is approximately 1.7～approximately 2.7; APS is the mean particle size with the fluidized-bed of inches; SBD is with lb/ft 3The deposition density of the polymer beads of this of meter; And SGV is the gas velocity in the fluidizing medium of ft/ second.The method comprises that also operating air Auto-regulating System of Density of Heavy Medium with fluidizing medium is to being less than or equal to critical gas density.The adjusting of operating air density has increased the tap density of fluidized-bed.
The conditioning period that the method is included in operating air density remains on fluidized-bed at least under turbulence state (turbulent regime).The method can also comprise fluidized-bed is moved to the turbulence state from fast fluidized condition.This has improved the tap density of this bed.
In embodiment, adjusting can be undertaken by the dividing potential drop of regulating contained gas in fluidizing medium, composition or the conditioned reaction device pressure of adjusting/change fluidizing medium.
In embodiment, fluidizing medium comprises propylene gas and at least a other gas.The method comprises fluidized-bed remained on turbulence state at least, and reduces the partial pressure of propylene of fluidizing medium, improves thus the tap density of fluidized-bed.Partial pressure of propylene can reduce individually, perhaps carries out with the velocity composition ground that reduces fluidizing medium.
In embodiment, the method comprises operating air density from being reduced to lower than critical gas density higher than critical gas density.Improved like this tap density of fluidized-bed.
In embodiment, provide another kind of polymerization process.The method is at one or more alkene of Gas-phase reactor polymerization.This reactor has fluidized-bed and fluidizing medium.This fluidizing medium has operating air speed.The method comprises the critical gas speed that is identified for fluidizing medium.Adopt following formula to determine this critical gas speed:
a × APS × SBD ( FMD ) 1 / b
Wherein, a is constant, and its value is approximately 3.5～approximately 6.2; B is constant, and its value is approximately 1.7～approximately 2.7; APS is the mean particle size with the fluidized-bed of inches; SBD is with lb/ft 3The deposition density of the polymer beads of this of meter, FMD is with lb/ft 3The density of the fluidizing medium of meter.The method comprises the operating air speed setting to being less than or equal to critical gas speed.At this conditioning period, fluidized-bed is remained at least under the turbulence state.The adjusting of operating speed can comprise makes fluidized-bed move to the turbulence state from fast fluidized condition.
In embodiment, begin the adjustment operation gas velocity from the speed greater than critical gas speed, and it is reduced to be less than or equal to critical gas speed.Improved like this tap density of fluidized-bed.
In embodiment, the method comprise with operating air speed from greater than the speed setting of Uk to the speed lower than Uk.Improved like this tap density of fluidized-bed.Operating air speed is remained on speed greater than Uc.
Present disclosure provides another kind of method.In embodiment, provide the method that is used at one or more alkene of Gas-phase reactor polymerization.This reactor has fluidized-bed and fluidizing medium.This fluidizing medium has operating air density and operating air speed.The method comprises the critical gas speed that is identified for this fluidizing medium according to following formula:
a × APS × SBD ( FMD ) 1 / b
Wherein, a is constant, and its value is approximately 3.5～approximately 6.2; B is constant, and its value is approximately 1.7～approximately 2.7; APS is the mean particle size of fluidized-bed; SBD is the deposition density of fluidized-bed; FMD is the density of fluidizing medium.The method comprises regulates this operating air density or operating air speed, makes this operating air speed be less than or equal to critical gas speed.
In embodiment, the method comprises the adjustment operation gas density, and the adjustment operation gas velocity.Carry out these adjustings, make this operating air speed be less than or equal to critical gas speed.
In embodiment, this fluidizing medium comprises propylene gas and at least a other gas.The method comprises the dividing potential drop that reduces propylene gas.This adjusting has improved the tap density of fluidized-bed.
In embodiment, the method comprise make operating air speed from greater than the Speed Reduction of critical gas speed to the speed less than critical gas speed.Improved like this tap density of fluidized-bed.
Present disclosure provides a kind of device.In embodiment, provide gas-phase polymerization reactor.This Gas-phase reactor comprises the fluidized-bed by the polymer beads of fluidizing medium fluidisation.The mean particle size of this polymer beads is approximately 0.014 inch to approximately 0.12 inch.The tap density of this fluidized-bed is about 7lb/ft 3～about 40lb/ft 3This fluidizing medium has the operating air density that is less than or equal to critical gas density, and this critical gas density is as above determined.This fluidizing medium also can have the operating speed that is less than or equal to critical gas speed as discussed above.This fluidized-bed is in turbulence state at least.
In embodiment, this gas-phase polymerization reactor is included in catalyst composition and at least a olefin gas of Gas-phase reactor inside.The polymer beads that is formed by this polymerization can be based on the polymkeric substance of propylene, based on polymkeric substance and the ethylene/propylene rubber of ethene.The deposition density of this polymer beads is about 15lb/ft 3～about 35lb/ft 3
In embodiment, the speed of this fluidizing medium is about 2.6ft/ second 0.5ft/ second～approximately.The density of this fluidizing medium is about 1.0lb/ft 3～about 5.0lb/ft 3
In embodiment, this fluidizing medium comprises propylene and hydrogen.The dividing potential drop of propylene is the about 400psia of 300psia～approximately.
In the application, disclosed any method can comprise catalyst composition is incorporated in reactor, forms thus mean particle size and be approximately 0.014 inch to the about fluidized-bed of 0.12 inch.
In the application, disclosed any method can comprise that making deposition density is about 15lb/ft 3～about 35lb/ft 3Polymer beads.
In the application, disclosed any method can comprise and makes fluidizing medium pass through reactor with the speed of 5.0ft/ second about 0.8ft/ second～approximately.
In the application, disclosed any method can comprise the tap density of fluidized-bed is improved approximately 10wt% to about 100wt%.This tap density increase is based on the tap density before regulating.
Present disclosure provides improving one's methods for the vapour phase polymerization of one or more alkene.
The advantage of present disclosure is to increase productivity by the tap density that improves fluidized-bed.
The advantage of present disclosure is can be when improving fluidized-bed and piling up density, has the risk that seldom or not has in flakes, becomes piece, overheated, bed collapse and/or reactor shutdowns.
The advantage of present disclosure is to need not to increase the gas phase polymerization process that reactor residence time can improve productivity.
Description of drawings
Fig. 1 is the diagram according to the gas velocity of the embodiment of present disclosure (SGV) and partial pressure of propylene.
Fig. 2 is the diagram according to the fluidisation tap density of the embodiment of present disclosure and bed weight.
Detailed Description Of The Invention
In embodiment, provide the method that is used at one or more alkene of Gas-phase reactor polymerization.This Gas-phase reactor comprises fluidized-bed and fluidizing medium.This fluidizing medium has operating air density.The method comprises the critical gas density that is identified for this fluidizing medium, and with this operating air Auto-regulating System of Density of Heavy Medium to being less than or equal to this critical gas density.
" vapour phase polymerization " used in the application is under the existence of catalyzer, makes up fluidizing medium (ascending fluidizing medium) (this fluidizing medium contains one or more monomers) through remained on the polymer beads fluidized-bed under fluidized state by this fluidizing medium." rheomorphism ", " fluidisation " or " fluidisation " are gas-solid contact processes, and wherein the bed of finely divided polymer beads promotes and stirs by upstream.When the fluid that flows by the rising in grain bed space obtained to surpass the pressure reduction of particle weight and friction resistance increment, rheomorphism occured in grain bed.Thus, " fluidized-bed " is to be suspended in a plurality of polymer beads under fluidized state by fluidizing medium stream." fluidizing medium " is one or more olefin gas, randomly contains carrier gas (such as H 2Or N 2) and randomly contain up liquid (such as hydrocarbon) by this Gas-phase reactor.
Typical gas-phase polymerization reactor (or Gas-phase reactor) comprises that container (being reactor), fluidized-bed, grid distributor, entrance and exit pipeline, compressor, recycle gas water cooler or interchanger and product discharge system.This container comprises reaction zone and deceleration area, all is positioned on grid distributor separately.Berth is in reaction zone.In embodiment, this fluidizing medium comprises that propylene gas and at least a other gas such as alkene and/or carrier gas are such as hydrogen or nitrogen.
Monitor and control many operating parameterss during vapour phase polymerization.A kind of parameter is the fluidisation tap density." fluidisation tap density " (or FBD) is the weight of the solid (being polymer beads) of unit volume in fluidized-bed.FBD is the mean value that can be greater than or less than the local accumulation density of any point in the fixed reactor part.FBD is the direct indication of Gas-phase reactor operational stage.The unexpected variation of FBD often represents that this reactor is just experiencing problem.
Usually, with the hypomere of catalyst charge to reactor.React when catalyzer contacts with fluidizing medium, produce the polymer beads that increases.Fluidizing medium is provided for the medium of heat exchange and rheomorphism upwards by fluidized-bed.This reactor comprises the extension (expandedsection) that is positioned on conversion zone.In the extension, final velocity is separated (disentrain) greater than the particle of fluidizing medium speed from fluidizing medium stream.After leaving reactor, fluidizing medium was removed the polymerization heat thus by compressor and one or more interchanger before the conversion zone of it being introduced again reactor.After cooling and condensation, fluidizing medium can contain or can not contain a certain amount of liquid.
Can introduce one or more olefinic monomers in Gas-phase reactor so that itself and catalyst reaction, and form the fluidized-bed of polymkeric substance or polymer beads.The non-limiting example of suitable alkene comprises ethene, propylene, C 4-20Alpha-olefin is such as C 4-12Alpha-olefin such as 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecylene etc.; C 4-20Diolefine is such as 1,3-butadiene, 1,3-pentadiene, norbornadiene, 5-ethylidene-2-norbornene (ENB) and Dicyclopentadiene (DCPD); C 8-40Vinyl aromatic compounds comprises vinylbenzene, o-methyl styrene, a vinyl toluene and p-methylstyrene, Vinylstyrene, vinyl biphenyl, vinyl naphthalene; C with the halogen replacement 8-40Vinyl aromatic compounds is such as chlorostyrene and fluorostyrene.
Any olefin polymerization catalysis can be incorporated in Gas-phase reactor.This catalyzer can add with the form of solid, slurry or solution, and can load on inorganic or organic carrier.This catalyzer can be prepolymer.Can adopt gas, liquid or gas/liquid mixture (the liquefaction cycle gas that comprises condensation in for example gaseous ethylene, nitrogen, recycle gas and propane or petrogas, propylene, iso-pentane and circulation loop) with this catalyst transport to reactor.Catalyzer can be incorporated in reactor individually or with fluidizing medium in combination.
" catalyst composition " that uses in the application is the composition that forms when contacting with one or more alkene under polymerizing condition based on the polymkeric substance of alkene." polymerizing condition " is to be suitable for promoting polymerization between catalyzer and alkene with the temperature and pressure parameter of the polymkeric substance that forms expectation within polymerization reactor.This catalyst composition can randomly comprise promotor, interior electron donor(ED), external electronic donor, selective control agent and any combination thereof.The non-limiting example of suitable catalyst composition comprises Ziegler-Natta catalyst composition, constrained geometry catalyst composition and metallocene catalyst compositions.
In embodiment, this catalyst composition is the Ziegler-Natta catalyst composition." the Ziegler-Natta catalyst composition " that uses in the application is transistion metal compound (procatalyst, the combination of the organometallic compound (promotor) of procatalyst) and (2) periodictable the I～III family metal of (1) periodic table of elements the IV～VIII family element.The non-limiting example of suitable Ziegler-Natta procatalyst comprises halogenide or the oxidative halogenation thing (oxyhalide) of titanium, vanadium, chromium, molybdenum and zirconium.The non-limiting example of Ziegler-Natta promotor comprises hydride, alkylide or the arylide of aluminium, lithium, zinc, tin, calcium, beryllium and magnesium.
In embodiment, can adopt procatalyst precursor (it comprises the magnesium part) to form procatalyst compositions.The source that is used for this magnesium part comprises the alkoxyl group magnesium halide of Magnesium Chloride Anhydrous, alkoxyl magnesium or aryloxy magnesium, mixing or dialkoxy magnesium or the aryloxy magnesium of carbonic acid esterification.The non-limiting example that magnesium is partly originated is two-(C 1-4) alkoxyl magnesium, particularly diethoxy magnesium.In addition, this precursor can comprise the titanium part.Suitable source comprises titan-alkoxide, aryloxy titanium, alkoxyl group halogenated titanium and halogenated titanium.Precursor can comprise one or more two-(C 1-4) alkoxyl magnesium and one or more four-(C 1-4) titan-alkoxide.
The whole bag of tricks of preparation procatalyst precursor is as known in the art.Especially, this preparation comprises the halogenation of magnesium and the titanium alcoxylates of aforementioned mixing, and one or more help to form the compound (being called " clip agent (clippingagent) ") of the specific lower molecular weight composition of expecting form can to comprise use.The example of suitable clip agent comprises particularly triethyl-boron acid esters of trialkylboron acid esters, and phenolic compound is cresylol particularly, and silane.
In embodiment, this procatalyst precursor is to have formula Mg dTi (OR e) eX fMixed type magnesium/titanium compound (MagTi), R wherein eBe aliphatics or aromatic hydrocarbyl or the COR ' with 1～14 carbon atom, wherein R ' is aliphatics or the aromatic hydrocarbyl with 1～14 carbon atom; Each ORe group is identical or different; X is chlorine, bromine or iodine independently, preferred chlorine; D is 0.5～56 or 2～4; E is 2～116 or 5-15; And f is 3～116 or 1～3.This precursor prepares by controlled precipitation, by remove alcohol from the reaction mixture that uses their preparation.In embodiment, reaction medium comprises the mixture of aromatics liquid (particularly chloro aromatic substance, chlorobenzene) the most especially and alkanol (particularly ethanol).Suitable halide reagent comprises titanium tetrabromide, titanium tetrachloride or titanous chloride, particularly titanium tetrachloride.Remove alkanol from the solution that halogenating reaction is used, cause having the precursor precipitation of the solid of the form of special expectation and surface-area.In addition, the precursor that obtains is uniform especially aspect granularity.
This precursor is by further reacting (halogenation) (step C) and in conjunction with interior electron donor(ED), being converted into solid procatalyst with halide reagent.Suitable halide reagent is for having formula Ti (OR e) eX hTitanium halide, R wherein e, X and e as defined above; H is integer 1～4; And e+h is 3 or 4.In embodiment, halide reagent is TiCl 4In embodiment, carry out halogenation under the existence of halogenated aromatic liquid such as dichlorobenzene, ortho-chlorotolu'ene or chlorobenzene.In embodiment, comprise 40～60 volume % halide reagents such as TiCl by use 4Halide reagent and the mixture of chlorinating aromatic liquid carry out this halogenation.
As required, can the reacting by heating mixture during (step C).In embodiment, at first precursor and halide reagent contacted at the temperature of 0～60 ℃ or 20～30 ℃, and heat with the speed of 0.1～10.0 ℃/min or 1.0～5.0 ℃/min.Produce in order to reduce particulate after first contact phase between halide reagent and precursor, can add interior electron donor(ED) subsequently.The halogenation temperature is 60～150 ℃ (any value or subranges perhaps), is perhaps 90～120 ℃.Halogenation can substantially not exist in the situation of electron donor(ED) to be carried out 5～60 minutes or 10～50 minutes.
Interior electron donor(ED) can be carboxylicesters, diether, succinate, dialkoxy benzene or diol ester.In embodiment, in this, electron donor(ED) is carboxylicesters, such as the C of aromatic dicarboxylic acid 1-10The C of alkyl diester, particularly phthalic acid or terephthalic acid 1-4Alkyl diester.The non-limiting example of suitable carboxylicesters comprises diethyl phthalate, diisopropyl phthalate, diisobutyl phthalate, terephthalic acid diisopropyl ester and isobutyl terephthalate.As required, can adopt the mixture of aforesaid compound.In embodiment, interior electron donor(ED) is diisobutyl phthalate.Enough interior electron donor(ED)s are provided usually, making the interior electron donor(ED) that exists in the solid procatalyst precursor in this stage of preparation and the mol ratio of magnesium is approximately 0.01: 1～approximately 1: 1, perhaps approximately 0.05: 1～approximately 0.5: 1, perhaps approximately 0.03: 1～approximately 0.1: 1.
The mode that procatalyst precursor, halide reagent and interior electron donor(ED) are contacted can change.In embodiment, at first make the procatalyst precursor and contain the mixture of halogenation reagent with the chloro aromatic substance and contact.Obtaining mixture is stirred, and can be heated as required.Subsequently, interior electron donor(ED) is added in the same reaction mixture, and does not separate or reclaim precursor.Aforementioned technique can adopt the various compositions of being controlled by the automatic controlling device to add, and carries out in single reactor.
The duration of contact of precursor and interior electron donor(ED) in the temperature of at least 25 ℃ or at least 50 ℃ or at least 60 ℃ to 150 ℃ or 120 ℃ or be at least 10 minutes or at least 15 minutes or at least 20 minutes or at least 1 hour at the temperature of 115 ℃ at the most at the most at the most.
Subsequently resulting precursor is reclaimed, in the situation that do not have interior electron donor(ED) and the halide reagent mixture in the chloro aromatic substance, in the temperature of at least 25 ℃ or at least 50 ℃ or at least 60 ℃ to 150 ℃ or 120 ℃ or at the most at the temperature of 115 ℃ at the most at the most, contact one or many (step D) reaches at least 10 minutes or at least 15 minutes or at least 20 minutes, and 1 hour or 45 minutes or 30 minutes at the most at the most at the most.
After aforementioned halogenation operation, the reaction medium that adopts in obtaining solid procatalyst composition and last process is separated, for example by filtering, make thus wet cake.This wet cake liquid dilution agent can be rinsed or washed to remove unreacted TiCl subsequently 4, and can be dried to remove as required residual liquid.Usually, the solid procatalyst composition that exchanged is washed one or many with " washing lotion " (it is that liquid hydrocarbon is such as aliphatic hydrocarbon such as iso-pentane, octane-iso, isohexane, hexane, heptane or octane).The solid procatalyst composition that exchanged can be separated subsequently and dry, perhaps at hydrocarbon, particularly than heavy hydrocarbon such as mineral oil in slurry, be used for further storing or using.
The solid procatalyst composition that obtains is the form of porous particle, and its titanium content is the about 6.0wt% of 0.1wt%～approximately, based on the solid gross weight; Be perhaps the approximately 4.5wt% of 1.0wt%～approximately or the approximately 3.5wt% of 1.5wt%～approximately.In the solid procatalyst composition that exchanged the weight ratio of titanium and magnesium be suitably approximately 1: 3～approximately 1: 160, perhaps approximately 1: 4～approximately 1: 20, perhaps approximately 1: 6～1: 13.In in this procatalyst compositions, electron donor(ED) can be take the mol ratio of interior electron donor(ED) and magnesium as approximately 0.005: 1～approximately 1: 1 or approximately 0.04: 1～approximately existence in 0.4: 1.
In embodiment, with the application's procatalyst and formula Mg dTi (OR e) eX f(ED) gMixed magnesium/titanium compound mix, R wherein eBe aliphatics or aromatic hydrocarbyl or the COR ' with 1～14 carbon atom, wherein R ' is aliphatics or the aromatic hydrocarbyl with 1～14 carbon atom, each R eGroup is identical or different; X is chlorine, bromine or iodine independently; ED is interior electron donor(ED), such as diisobutyl phthalate; D be 0.5～56, e be 0,1 or 2, f be 3～116, and g is 0.005d～1d.
This procatalyst compositions can further be processed by one or more following operations before or after separating this solid procatalyst.Can make as required this procatalyst compositions contact (halogenation) with other a certain amount of titanium halide; It is exchanged such as phthalyl chloride or Benzoyl chloride with acyl chlorides under the metathesis condition, and can be with its flushing or cleaning, thermal treatment; Perhaps slaking (aged).Aforementioned additional process can be with any sequential combination or is adopted individually, does not perhaps adopt.
Do not expect to be subject to the restriction of any concrete theory, think and contact with titanium halide (the particularly solution of titanium halide in halocarbon diluent) the further halogenation of carrying out by the procatalyst compositions that makes previous formation, causing the improvement of this procatalyst compositions expectation, may be to have removed some the inert metal compounds (inactive metal compound) that dissolve in aforementioned thinner.Thus, in embodiment, make this procatalyst and halide reagent such as titanium halide and halocarbon diluent (TiCl for example 4With chlorobenzene) separate or reclaim before contact one or many.
This promotor can be selected from any known activator of the olefin polymerization catalyst system that adopts titanium halide or organo-aluminium compound.The limiting examples of suitable promotor comprises trialkyl aluminium compound, aluminum alkyls alkoxy compound, comprise the aikyiaiurnirsoxan beta of oligomeric or polymerization or pass through in conjunction with one or more different trialkyl aluminium compounds the modified version aikyiaiurnirsoxan beta of modification, and aluminum alkyl halide.In embodiment, the compound of aforementioned series contains alkyl, and wherein each alkyl has 1～6 carbon atom independently.In another embodiment, this promotor is trialkylaluminium or dialkyl aluminum halide, and wherein each alkyl contains 1～4 carbon atom independently.In another embodiment, this promotor is triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, diethyl aluminum chloride or its mixture.This promotor take aluminium/titanium mol ratio as approximately 1: 1～approximately the amount of 500: 1 or approximately 10: 1～approximately 200: 1 or approximately 35: 1～approximately 50: 1 adopts.
In embodiment, this catalyst composition comprises external donor, and it is the mixture of active restriction agent (activitylimiting agent, ALA) and selective control agent (selectivity control agent, SCA).ALA is aromatic carboxylic acid's ester or derivatives thereof, aliphatic ester, perhaps non-ester component (non-estercomposition).The non-limiting example of suitable aromatic carboxylic acid ester comprises aromatic monocarboxylate's C 1-10The alkyl or cycloalkyl ester.Its suitable substitutive derivative is included in aromatic ring or ester group is both gone up the compound of the one or more substituting groups replacements that contained one or more the 14th, 15 or 16 family's heteroatomss (particularly oxygen).This substituent example comprises (gathering) alkyl oxide, cycloalkyl ethers, aryl ethers, aralkyl ethers, alkyl thioether, aryl thioethers, dialkylamine, diarylamine, two aralkylamines and trialkylsilanyl group.This aromatic carboxylic acid ester can be benzoic C 1-20Hydrocarbyl carbonate, wherein this alkyl be unsubstituted or replace have one or more contain the 14th, the 15 or 16 heteroatomic substituting groups of family with and C 1-20(gathering) hydrocarbyl ether derivative, perhaps phenylformic acid C 1-4Alkyl ester and C thereof 1-4The derivative of cycloalkylation (ringalkylated derivative), perhaps methyl benzoate, ethyl benzoate, propyl benzoate, p-methoxyl methyl benzoate, p-ethoxy-benzoic acid methyl ester, p-methoxybenzoic acid ethyl ester and p-ethoxy benzonitrile acetoacetic ester.In embodiment, this aromatic monocarboxylate's ester is p-ethoxy benzonitrile acetoacetic ester.
In embodiment, ALA is aliphatic ester.This aliphatic ester can be C 4-30Fatty acid ester can be monoesters or many (two or larger) ester, can be straight chain or branching, can be saturated or unsaturated, and any combination.This C 4-30Fatty acid ester also can be replaced by one or more the 14th, 15 or 16 heteroatomic substituting groups of family that contain.Suitable C 4-30The non-limiting example of fatty acid ester comprises aliphatics C 4-30The C of monocarboxylic acid 1-20Alkyl ester, aliphatics C 8-20The C of monocarboxylic acid 1-20Alkyl ester, aliphatics C 4-20The C of monocarboxylic acid and dicarboxylic acid 1-4The alkyl list-or diester, aliphatics C 8-20The C of monocarboxylic acid and dicarboxylic acid 1-4Alkyl ester and C 2-100(gathering) glycol or C 2-100The C of (gathering) glycol ethers 4-20The alkyl list-or the polycarboxylate derivative.In another embodiment, this C 4-30Fatty acid ester can be Isopropyl myristate, n-butyl sebacate, (gathering) (aklylene glycol) single-or diacetate esters, (gather) (aklylene glycol) single-or two myristinates, (gather) (aklylene glycol) singly-or dilaurate, (gathering) (aklylene glycol) single-or dioleate, glycerine three (acetic ester), C 2-40The triglyceride level of lipid acid, and composition thereof.In another embodiment, this C 4-30Aliphatic ester is Isopropyl myristate or n-butyl sebacate.
In embodiment, ALA is non-ester component." the non-ester component " used in the application is atom, molecule or the compound that does not contain ester functional group.In other words, should " non-ester component " not contain following functional group.
Figure GPA00001115291800101
In embodiment, this non-ester component can be dialkyl group diether compounds or amine compound.This dialkyl group diether compounds is expressed from the next,
Figure GPA00001115291800111
R wherein 1～R 4Be to have alkyl, the aryl or aralkyl of 20 carbon atoms at the most independently of one another, it can randomly contain the 14th, 15,16 or 17 family's heteroatomss, and prerequisite is R 1And R 2It can be hydrogen atom.the non-limiting example of suitable dialkyl ether compounds comprises dimethyl ether, Anaesthetie Ether, dibutyl ether, methyl ethyl ether, methyl butyl ether, methylcyclohexyl ether, 2, 2-dimethyl-1, the 3-Propanal dimethyl acetal, 2, 2-diethyl-1, the 3-Propanal dimethyl acetal, 2, 2-di-n-butyl-1, the 3-Propanal dimethyl acetal, 2, 2-Di-Isobutyl-1, the 3-Propanal dimethyl acetal, 2-ethyl-2-butyl-1, the 3-Propanal dimethyl acetal, 2-n-propyl-2-cyclopentyl-1, the 3-Propanal dimethyl acetal, 2, 2-dimethyl-1, the 3-di ethyl propyl ether, 2-sec.-propyl-2-isobutyl--1, the 3-Propanal dimethyl acetal, 2, 2-two cyclopentyl-1, the 3-Propanal dimethyl acetal, 2-n-propyl-2-cyclohexyl-1, the 3-di ethyl propyl ether, with 9, two (methoxymethyl) fluorenes of 9-.In another embodiment, this dialkyl ether compounds is 2,2-di-n-butyl-1, the 3-Propanal dimethyl acetal.
In embodiment, this non-ester component is amine compound.The non-limiting example of suitable amine compound comprises the piperidines that 2,6-replaces, such as the piperidines of lupetidine and 2,2,6,6-tetramethyl piperidine and 2,5-replacement.In another embodiment, this piperidine compounds is 2,2,6,6-tetramethyl piperidine.
SCA comprises silane.Silane can comprise having general formula SiR m(OR ') 4-m(I) one or more organoalkoxysilanes, hydrogen or alkyl or amino independently when wherein R occurs at every turn, randomly contained one or more the 14th, 15,16 or 17 heteroatomic substituting groups of family and replace, R contains 20 atoms (not including hydrogen and halogen interior) at the most, and R ' is C 1-20Alkyl, and m is 0,1,2 or 3.In embodiment, R is C 6-12Aryl, alkyl or aralkyl, C 3-12Cycloalkyl, C 3-12Branched-alkyl, or C 3-12Cyclic amino, R ' are C 1-4Alkyl, and m is 1 or 2.the non-limiting example of suitable silane components comprises dicyclopentyl dimethoxyl silane, two-tertiary butyl dimethoxy silane, Cyclohexylmethyldimethoxysilane, ethyl cyclohexyl dimethoxy silane, dimethoxydiphenylsilane, diisopropyl dimethoxy silane, two-n-propyl dimethoxy silane, second, isobutyl dimethoxy silane, di-n-butyl dimethoxy silane, cyclopentyl-trimethoxy-silane, the sec.-propyl Trimethoxy silane, the n-propyl Trimethoxy silane, the n-propyl triethoxyl silane, ethyl triethoxysilane, tetramethoxy-silicane, tetraethoxysilane, cyclopentyl dimethylamino pyrrolidinyl TMOS, two (pyrrolidyl) dimethoxy silane, two (perhydro isoquinolyl) dimethoxy silane, dimethyldimethoxysil,ne, the tetraethyl orthosilicate ester, the positive silicon ester of tetramethyl-, with the positive silicon ester of tetramethoxy oxyethyl group.In embodiment, this silane components is dicyclopentyl dimethoxyl silane, Cyclohexylmethyldimethoxysilane or n-propyl Trimethoxy silane and any combination thereof.In another embodiment, this silane is dicyclopentyl dimethoxyl silane.
The bed of polymer particles that vapour phase polymerization requires the speed of fluidizing medium should be enough to form remains under fluidized state.The speed of fluidizing medium is also referred to as superficial gas velocity." superficial gas velocity " used in the application (or " SGV ") is that fluidizing medium is through the tolerance of the flow velocity of reactor.SGV is by calculating the recycle gas volumetric flow rate divided by cross-sectional reactor area.Suitable fluidisation for grain bed needs minimum SGV.In the condensing mode operation of gas-phase polymerization reactor, need minimum SGV so that condensed fluid is carried to reactor from interchanger.Term " fluidizing medium speed " and " superficial gas velocity " are used interchangeably.
In embodiment, the product that makes in gas-phase polymerization reactor is based on the polymkeric substance (alfon, propylene/olefin copolymer) of propylene, based on polymkeric substance (Alathon, ethylene/olefin interpolymers) or the ethylene/propylene rubber of ethene.
Fluidized-bed allow with heat from the growth polymer beads be delivered to rapidly fluidizing medium.Fluidizing medium can be from reactor recycled/recovered to remove heat from this system.Fluidized-bed also can make reactant be delivered to rapidly the active catalyst site, has improved the useful efficiency of catalyzer.Reactor can be vapor condensation Pattern Aggregation reactor.
The structure of fluidized-bed changes with SGV.Known following fluidized state (SGV arranges from low to high): (i) fixed bed, (ii) minimum fluidized voidage, (iii) quiescent fluidization, (iv) bubbling fluidization, (v) turbulence fluidization, (vi) transportation, and (vii) pneumatic transport.Every kind of fluidized state has the specific characteristic that is different from various other states.For example, the turbulence state is not to be the regular concentrated phase bed (dense bed) with bubbling fluidization state of freeboard of fluidized bed behavior in fact (freeboard activity) simply.Thus, the model for a kind of state may not must be applicable to another state.For example, model and the dependency number (correlation) for bubbling fluidization state or fast fluidized condition exploitation may and not be suitable for the turbulence fluidized state.
Fluidized state can be distinguished by Bubble Characteristics (bubble behavior).The bubbling fluidization state shows recognizable bubble.Control the bubble phase mutual effect by merge bubble under the bubbling fluidization state.
The feature of " turbulence state " or " turbulence fluidization " is to have many little bubble/cavities, wherein merges with respect to bubble, and bubble-break accounts for main trend.The turbulence fluidization occurs when beginning to lose their shapes near the bed top when most of bubble, and the turbulence campaign appearance in the gas group of various size and shape (cluster of gas) and cavity.Turbulence state bubble is division and restructuring often, the out-of-shape of these bubbles (having unsharp border) and often be called " gas cavity " or " cavity ".Sharply moving in bubble/cavity, makes the external phase and the disperse phase that are difficult to distinguish in bed.When under the turbulence state, SGV is higher, reach fast fluidization along with gas velocity further increases, the clear boundary in bubble/cavity disappears, and the distribution of inhomogeneous solids concn produces the gas cavity of undistinguishable more that becomes.Along with superficial gas velocity increases, the fluidised appearance of turbulence is associated with transition speed (transition velocity).In fluidized-bed, pressure surge disappears when SGV is elevated to a fixed point." transition speed " that uses in the application or " Uc " are the SGV that the mean amplitude of tide (mean amplitude) at pressure surge peak is located.Transition speed Uc has also distinguished the appearance (with the bubbling state) of turbulence state.Think that the turbulence fluidization can not exist equably in the vertical dimension of bed.
" fast fluidization " or " fast fluidized condition " be characterised in that, for the fluidizing medium of equal flow rates and density, is to inject the monotonic quantity of the amount of solid along the pressure gradient of throughput direction.The turbulence fluidization is given way in (yield to) fast fluidization when bubble and cavity are reduced to the same order of solid particulate dimensionally." transfer rate " used in the application or " Uk " are the beginnings of the fluidised termination of turbulence and fast fluidization when superficial gas velocity increases.Uk is the SGV that distinguishes the beginning of the fluidised termination of turbulence and fast fluidization.Transfer rate is when gas velocity increases to over Uc, the gas velocity the when mean amplitude of tide of pressure surge is stablized.
Gas phase polymerization process comprises, is identified for the critical gas density of fluidizing medium, and with the operating air Auto-regulating System of Density of Heavy Medium of this fluidizing medium to being less than or equal to this critical gas density." the critical gas density " used in the application is the density of fluidizing medium when transition point.This " transition point " is the line of delimitation between turbulence fluidization and fast fluidization.Determine this critical gas density by following formula (I):
( a × APS × SBD SGV ) b
Wherein a is constant, and its value is approximately 3.5～approximately 6.2; B is constant, and its value is approximately 1.7～approximately 2.7; APS is the mean particle size of fluidized-bed; SBD is the deposition density of fluidized-bed; And SGV is the superficial gas velocity of fluidizing medium.In embodiment, the value of a is approximately 4.3～approximately 5.6, and the value of b is approximately 1.9～approximately 2.5.
" the operating air density " used in the application is the gas density of fluidizing medium under reactor operating condition.The operating air density of this fluidizing medium is remained the critical gas density that is less than or equal to by following formula (II) measurement:
(II)
Wherein a and b are the constant with disclosed value in formula (I).
The applicant has found accurately to determine marginal model between turbulence state and fast fluidized condition surprisingly and against expectation.Parameter A PS, SBD and/or SGV affect the value of critical gas density.In other words, APS, SBD, SGV (and about a and b value) impact or determine in addition border between turbulence state and fast fluidized condition.
In embodiment, the application's gas phase polymerization process remains on speed greater than transition speed Uc with fluidizing medium.Thus, at least a portion (perhaps whole, or basically whole) fluidized-bed is in turbulence state at least during polymerization process.In embodiment, make fluidized-bed during the adjustment operation gas density and/or remain on afterwards at least under the turbulence state.In other words, the application's method before the adjustment operation gas density, among and/or operate on the bubbling fluidization state afterwards.In another embodiment, the fluidized-bed under fast fluidized condition and with the operating air Auto-regulating System of Density of Heavy Medium to being equal to or less than critical gas density, improved the tap density of fluidized-bed, and made fluidized-bed move to the turbulence state.
The adjusting of operating air density can be carried out in many ways.Can pass through dividing potential drop, (ii) adjusting or the composition that changes or change in addition fluidizing medium, (iii) adjusting Gas-phase reactor pressure and (iv) any combination of (i)～(iii) that (i) adjusting forms one or more gases of this fluidizing medium, the operating air density of fluidizing medium can be moved when being equal to or less than critical gas density, perhaps be set in addition be equal to or less than critical gas density.
In embodiment, this fluidizing medium contains propylene gas and at least a other gas.This other gas can be hydrogen, olefin gas (such as ethene, butylene or octene) and/or nitrogen.The method comprises remains at least under the turbulence state (some or all) fluidized-bed, and reduces the partial pressure of propylene of this fluidizing medium.When fluidized-bed was in fast fluidized condition, the reduction of partial pressure of propylene made the operation of operating air density or is set in addition be equal to or less than critical gas density.In addition, the reduction of partial pressure of propylene has improved the tap density of fluidized-bed.Reducing partial pressure of propylene causes the density of fluidizing medium to reduce.Do not expect to be subject to the restriction of any concrete theory, think that it (is that gas density * SGV), it has reduced the lifting force on the bed, allows thus a compacting that reduction fluidizing medium density has reduced the fluidizing medium momentum.Before the bed of compacting reduces with respect to fluidizing medium density, uncompacted bed accessory has the FBD of increase.
In embodiment, the partial pressure of propylene of fluidizing medium can reduce individually or combine with the reduction of fluidizing medium speed, makes thus operating air density be set to be equal to or less than critical gas density.So also improved the tap density of fluidized-bed.
In embodiment, can change the composition of fluidizing medium with adjustments of gas density.For example, can be by use hydrogen exchange nitrogen, the forming of the fluidizing medium that change is comprised of olefin gas and nitrogen.This variation from nitrogen to hydrogen can change the dividing potential drop of olefin gas and/or change the density of fluidizing medium.In another embodiment, can change, regulate and/or change whole reactor pressure to change the operating air density of fluidizing medium.
In embodiment, this polymerization process comprises catalyst composition is incorporated in reactor, to form the polymer beads that forms fluidized-bed.This catalyst composition can be disclosed any catalyst composition in the application.The mean particle size of this polymer beads (APS) is approximately 0.014 inch～approximately 0.12 inch, perhaps approximately 0.018 inch～approximately 0.03 inch.In another embodiment, the deposition density (SBD) of this polymer beads is about 15lb/ft 3～about 35lb/ft 3
In embodiment, fluidizing medium flows through with the speed of 5.0ft/s of about 0.8ft/s～approximately or in addition by this bed.
In embodiment, the adjusting of operating air speed makes the tap density of fluidized-bed improve approximately 10wt% to about 100wt%, perhaps improves approximately 20% to approximately 50%.This FBD increase is based on the operating air Auto-regulating System of Density of Heavy Medium FBD of this bed before.
In embodiment, provide the other method that is used at one or more alkene of Gas-phase reactor polymerization.This Gas-phase reactor has fluidized-bed and fluidizing medium.The method comprises the critical gas speed that is identified for this fluidizing medium, and with the operating air speed setting of this fluidizing medium to being less than or equal to this critical gas speed." the critical gas speed " used in the application is the density of fluidizing medium when transition point.This " transition point " is the line of delimitation between turbulence fluidization and fast fluidization.Determine this critical gas density by following formula (III):
a × APS × SBD ( FMD ) 1 / b - - - ( III )
Wherein, a is constant, and its value is approximately 3.5～approximately 6.2, and b is constant, and its value is approximately 1.7～approximately 2.7, and APS is the mean particle size of fluidized-bed, and SBD is the deposition density of fluidized-bed, and FMD is fluidizing medium density.In embodiment, the value of a is approximately 4.3～approximately 5.6, and the value of b is approximately 1.9～approximately 2.5.
" the operating air speed " used in the application is the gas velocity of fluidizing medium under reactor operating condition.The operating air speed of this fluidizing medium is remained is less than or equal to by the definite critical gas speed of following formula (IV):
Figure GPA00001115291800152
Wherein a and b are the constant with disclosed value in formula (I).
Parameter A PS, SBD and/or FMD (and a and b) affect the value of this critical gas speed.In embodiment, this operating air speed remains on the speed greater than Uc.
In embodiment, the method is included in conditioning period fluidized-bed is remained at least under the turbulence state.This can comprise operating air speed is remained on speed greater than Uc.Improved like this FBD.Do not expect to be subject to the restriction of any concrete theory, think that the reduction of operating air speed has reduced the density of fluidizing medium.It (is that gas density * SGV), it has reduced the lifting force on the bed, allows thus a compacting that reduction fluidizing medium density has reduced the fluidizing medium momentum.
In embodiment, the method comprise with operating air speed from greater than the speed setting of critical gas speed to being less than or equal to critical gas speed.Improved like this tap density of fluidized-bed.For example, during greater than critical gas speed, fluidized-bed can be in fast fluidized condition when operating air speed.Control this moment or in addition adjustment operation speed so that some or all fluidized-beds be under fast fluidized condition.Thus, operating air speed can be greater than transfer rate Uk.The method comprises that reduction operating air speed is so that fluidized-bed moves to the turbulence state.
In embodiment, the method comprise with operating air speed from greater than the speed setting of Uk to the speed less than Uk.Improved like this SBD.
In embodiment, the method comprises that being incorporated into catalyst composition in reactor and forming APS is the approximately 0.014 inch～about fluidized-bed of 0.12 inch.This catalyst composition can be disclosed any catalyst composition in the application.The SBD of polymer beads is about 15lb/ft 3～about 35lb/ft 3
In embodiment, this fluidizing medium comprises that propylene gas and optional carrier gas are such as hydrogen and/or nitrogen.The gas density of this fluidizing medium is about 2.5lb/ft 3～about 5.0lb/ft 3The dividing potential drop of propylene gas can be about 300～approximately 400psia.
In embodiment, the adjusting of operating air density makes the tap density of fluidized-bed improve approximately 10wt% to about 100wt%, perhaps improves approximately 20% to approximately 50%.This raising is based on the FBD before the operating air speed setting.
In embodiment, provide another polymerization process.The method is for the polymerization process at one or more alkene of Gas-phase reactor polymerization.Gas-phase reactor has fluidized-bed and fluidizing medium.This fluidizing medium has operating air density and operating air speed.The method comprises the critical gas speed that is identified for this fluidizing medium based on above-mentioned formula (III), and adjustment operation gas density or operating air speed, makes operating air speed be less than or equal to critical gas speed.The adjusting of operating air density and/or operating air speed makes FBD improve approximately 10% to about 100% (based on the FBD before regulating).
In embodiment, the method comprises adjustment operation gas density and operating air speed simultaneously, makes operating air speed less than critical gas speed.
In embodiment, this fluidizing medium comprises propylene gas and at least a other gas.The method comprises the dividing potential drop that reduces propylene gas so that operating air speed is set to be equal to or less than critical gas speed.So also improved the tap density of fluidized-bed.
In embodiment, can reduce the density of fluidizing medium by reducing partial pressure of propylene, and also can reduce operating air speed so that operating air speed moves to lower than critical gas speed.Reduce simultaneously these parameters and improved FBD.At whole conditioning period, fluidized-bed is remained at least under the turbulence state.
In embodiment, the method comprise make operating air speed from greater than the Speed Reduction of critical gas speed to the speed less than critical gas speed.The reduction of operating air speed has improved the tap density of fluidized-bed.
In embodiment, the method comprises catalyst composition is incorporated in reactor, and to form APS be the about fluidized-bed of 0.014～approximately 0.12 inch.This catalyst composition can be disclosed any composition in the application.
In embodiment, the method comprises that making SBD is about 15lb/ft 3～about 35lb/ft 3Polymer beads.
The tap density of fluidized-bed that can make any preceding method improves 10% to approximately 100%, perhaps improves approximately 20% to approximately 80%, perhaps improves approximately 15% to 50%.The fluidized-bed that this increase is based on before reducing is piled up density.In embodiment, it is about 1lb/ft that any preceding method can produce FBD 3～about 40lb/ft 3, or about 7lb/ft 3～about 40lb/ft 3, or about 7lb/ft 3～about 35lb/ft 3Fluidized-bed.
Any preceding method can with approximately 28 tons/hour～approximately 35 tons/hour of 40 tons/hour or approximately 30 tons/hour～approximately or approximately the speed of 33 tons/hour produce polymkeric substance.Similarly, any preceding method can make the polymer particles less than 5wt%, the perhaps about 4wt% of 0.14wt%～approximately, and the perhaps about 3wt% of 14wt%～approximately is based on the weight of obtained polymkeric substance." polymer particles " that uses in the application is that maximum diameter is less than the polymer beads of 180 μ m (adopting the automatic particle size analyzer of Gradex 2000).
In embodiment, preceding method does not have a kind of the raising catalyst composition, olefin gas and/or the polymer beads residence time in reactor.Thus, present method has advantageously improved FBD, has improved productivity by the amount that has improved at the polymer product that makes before any process adjustments thus under same time.In other words, by improving FBD, present method need not to improve the production time and can make more voluminous thing.In embodiment, the residence time is approximately 0.5～approximately 2 hour, perhaps approximately 1 hour.
In embodiment, provide gas-phase polymerization reactor.This reactor comprises the fluidized-bed of polymer beads.The mean particle size of this polymer beads is approximately 0.014 inch～approximately 0.012 inch.The tap density of this fluidized-bed is about 1lb/ft 3～about 40lb/ft 3, or about 7lb/ft 3～about 35lb/ft 3This Gas-phase reactor also comprises fluidizing medium.This fluidizing medium has the operating air density that is less than or equal to by the definite critical gas density of above-mentioned formula (I).This fluidizing medium can also have the operating air speed that is less than or equal to by the definite critical gas speed of above-mentioned formula (III).This fluidized-bed is at least under the turbulence state.
In embodiment, this gas-phase polymerization reactor is included in catalyst composition and at least a olefin gas of this Gas-phase reactor inside.The polymer beads that forms due to polymerization can be based on the polymkeric substance of propylene, based on polymkeric substance and the ethylene/propylene rubber of ethene.The deposition density of this polymer beads can be about 15lb/ft 3～about 35lb/ft 3
In embodiment, this fluidizing medium speed is the about 2.6ft/s of 0.5ft/s～approximately.
In embodiment, this fluidizing medium comprises that propylene and at least a other gas are such as hydrogen or nitrogen.The density of this fluidizing medium is about 1.0lb/ft 3～about 5.0lb/ft 3, perhaps about 3lb/ft 3Partial pressure of propylene is the about 400psia of 300psia～approximately.
Definition
The periodic table of elements that in the application, all are mentioned refers to CRC Press, Inc., and 2003 publish and have the periodic table of elements of copyright.In addition, all one or more families of mentioning should be the IUPAC systems that adopt to be used for numbering these families in one or more families that this periodic table of elements reflects.Unless point out on the contrary, context hint, perhaps this area is commonly used, otherwise all umbers and per-cent are all based on weight.Purpose for the united states patent law practice, in the application, the content of all patents, patent application or the publication of reference is all introduced in the application (perhaps it being equal to the US version also is incorporated herein by reference like this) as a reference, particularly about the disclosure of synthetic technology, definition (its degree is not inconsistent with the definition that the application provides) and general knowledge known in this field.
The described any numerical range of the application comprise smaller value and higher value therebetween with all numerical value of an incremented, condition is to have the interval of at least two units between any smaller value and higher value.For example, physical properties or the mechanical properties (for example, molecular weight, viscosity, melt index etc.) as fruit component is 100 to 1000, mean clearly to have enumerated in this specification sheets whole single numerical value as 100,101,102 etc., and sub-range such as 100-144,155-170,197-200 etc.For containing less than 1 numerical value or greater than 1 the mark scope of (such as 1.1,1.5 etc.), think that aptly a unit is 0.0001,0.001,0.01 or 0.1.(for example, 1-5), it has been generally acknowledged that a unit is 0.1 for the scope that contains less than 10 number.These are only the examples of the concrete content that means, and might making up of cited Schwellenwert and the numerical value between maximum all is considered to clear record in this application.For weight percent, molecular weight and other character of density, component, put down in writing like that as discussed here in this application digital scope.
Term " comprises " and derivatives, is not to be the existence of getting rid of any other component, step or operation (with disclosed whether identical in the application).For fear of any query, by using term " to comprise " all claimed compositions, unless point out on the contrary, all can comprise any other additive, auxiliary agent or compound (no matter be polymkeric substance or other) in the application.On the contrary, term " basically by ... form " get rid of any other component, step or operation from the scope of any narration subsequently, except for operability be not requisite those.Term " by ... form " get rid of any component, step or the operation that do not specifically describe or list.The term "or", unless point out on the contrary, all the expression individually listed member with and any combination.
The term that uses in the application " blend " or " blend polymer " are the blends of two or more polymkeric substance.This blend can be miscible or immiscible (on molecular level, nothing is separated).That this blend can be separated or can not be separated.This blend can or can not contain one or more territories configuration, and it is measured by transmission electron microscope, scattering of light, X-ray scattering and other method known in the art.
The term that uses in the application " composition " comprises the mixture of the material that consists of said composition, and the reaction product and the degradation production that are formed by the material of said composition.
Term " polymer " " be the macromolecular cpd that is made by the monomer polymerization of identical or different type." polymkeric substance " comprises homopolymer, multipolymer, terpolymer, interpretation etc.The polymkeric substance that term " interpretation " the expression polymerization by at least two types of monomers or comonomer makes.Comprise but be not to be defined in multipolymer (often expression made by two kinds of dissimilar monomers or comonomer polymkeric substance), terpolymer (often expression made by three kinds of dissimilar monomers or comonomer polymkeric substance), tetrapolymer (often expression made by four kinds of dissimilar monomers or comonomer polymkeric substance) etc.
The polymkeric substance that the term that uses in the application " interpretation " expression is made by the polymerization of two kinds of dissimilar monomers at least.This generic term interpretation comprises multipolymer (be commonly used to represent made by two kinds of different monomers polymkeric substance), and the polymkeric substance that is made by two or more different monomers.
The term that uses in the application " polymkeric substance that contains ethene " expression comprises the polymkeric substance of the vinyl monomer (based on the gross weight of polymerisable monomer) of 0.1wt% polymerization at least, and randomly can comprise the comonomer of at least a polymerization.
The term that uses in the application " based on the polymkeric substance of propylene " expression comprises the polymkeric substance of propylene monomer (based on the gross weight of polymerisable monomer) of the polymerization of most of weight percent, and randomly can comprise the comonomer of at least a polymerization.
" productivity " is the polymer weight (being g polymkeric substance/g catalyzer) that the unit weight catalyzer that adopts in this polymerization technique makes.
Now infinite mode provides the embodiment of present disclosure with example.
Embodiment
Embodiment 1
Listed two kinds of different condition A and B operation polypropylene fluidized bed reactor in following table.Catalyst system is Zieglar-Natta type supported catalyst, contains simultaneously alkyl aluminum activator and external electronic donor.When changing condition from A to B, gas density is from 4.53lb/ft 3(A) be reduced to 4.00lb/ft 3(B) and SGV (A) be reduced to 1.20ft/s (0.37m/s) (B) from 1.27ft/s (0.39m/s).Due to the reduction of SGV, the critical gas density of being calculated by above-mentioned formula I is from 4.27lb/ft 3Bring up to 4.44lb/ft 3(wherein a=4.0 and b=2.3).During this process, by making propylene (C3H6) dividing potential drop from 393psi (27.6kg/cm 2) be reduced to 360psi (25.3kg/cm 2) reduce gas density (referring to Fig. 1).In situation A, gas density is greater than critical gas density, but in case B, gas density shows that less than critical gas density fluidized state is changed to turbulence (above-mentioned formula II) from fast fluidization.Due to the variation of this fluidized state, top fluidisation tap density has improved 25%, from 7.7lb/ft 3Bring up to 9.6lb/ft 3(from 124kg/m 3Bring up to 154kg/m 3), and bottom fluidisation tap density improved 21%, from 8.0lb/ft 3Bring up to 9.7lb/ft 3(from 128kg/m 3Bring up to 155kg/m 3) (referring to Fig. 2).The APS of the polymer powder of this embodiment is that about 0.025 inch and deposition density are 22～24lb/ft 3
Table 1
Reactor condition changes the impact general introduction on critical gas density and fluidisation tap density
Reactor condition A B
Temperature (℃) 65.5 65.5
Reactor pressure (psi) 469 440
Partial pressure of propylene (psi) 393 360
H 2Concentration (mol％) 0.2 0.2
C3H6 concentration (mol％) 81.4 79.4
C3H8 concentration (mol％) 6.3 6.9
N 2Concentration (mol％) 11.1 12.9
Gas density (lb/ft 3) 4.53 4.00
Superficial gas velocity (SGV) (ft/ second) 1.27 1.20
Tap density (SBD) (lb/ft 3) 24.1 22.5
Mean particle size (APS) (inch) 0.025 0.026
Critical gas density (lb/ft 3) 4.27 4.44
Top fluidisation tap density (kg/m 3) 124 154
Bottom fluidisation tap density (kg/m 3) 128 155
Bed is heavy (ton) 23.0 28.1
Fig. 1 is the graph of a relation of fluidisation tap density and bed weight.
Embodiment 2
Move polypropylene fluidized bed reactor under two different condition A and B, SGV is reduced to 0.87ft/s (B) from 1.30ft/s (A) during this period.All other reactor conditions roughly keep constant, comprise that gas density is in 2.82lb/ft 3Due to the reduction of SGV, the critical gas density of being calculated by above-mentioned formula I is from 2.19lb/ft 3Be increased to 7.00lb/ft 3(wherein a=4.0 and b=2.3).In situation A, gas density is greater than critical gas density, but in case B, gas density shows that less than critical gas density fluidized state changes to turbulence (above-mentioned formula II) from fast fluidization.The fluidisation tap density has improved 74%, from 5.5lb/ft 3(A) be increased to 9.6lb/ft 3(B).
Table 2
Figure GPA00001115291800211
Figure GPA00001115291800221
Fig. 2: the graph of a relation of fluidisation tap density and bed weight.
Explicitly pointing out present disclosure is not be defined in the embodiment that comprises in the application and illustrate, but comprise the improved form of these embodiments, comprise the combination of the unit of the part of these embodiments and different embodiments, as long as fall into the scope of claims.

Claims (12)

1. method that is used at one or more alkene of Gas-phase reactor polymerization, described Gas-phase reactor has fluidized-bed and possesses the fluidizing medium of operating air density, and the method comprises:
Adopt following formula to determine the critical gas density of fluidizing medium
( axAPSxSND SGV ) b
Wherein
A is constant, and its value is 4.0,
B is constant, and its value is 2.3,
APS is the mean particle size with the fluidized-bed of inches,
SBD is with lb/ft 3The deposition density of the polymer beads of this of meter,
SGV is the gas velocity in the fluidizing medium of ft/ second; With
With the operating air Auto-regulating System of Density of Heavy Medium of fluidizing medium to being less than or equal to described critical gas density.
2. the method for claim 1, it is included in conditioning period fluidized-bed is remained on turbulence state at least.
3. the process of claim 1 wherein that this adjusting is selected from the partial pressure of regulating fluidizing medium, the composition of regulating fluidizing medium, conditioned reaction device pressure and combination thereof.
4. the method for any one in claim 1～3, wherein this adjusting comprises and makes fluidized-bed run to the turbulence state from fast fluidized condition.
5. the method for any one in claim 1～3, it comprises fluidized-bed is remained on turbulence state at least, and regulates by this tap density that improves fluidized-bed.
6. the method for claim 1, it comprises makes fluidized-bed move to the turbulence state from fast fluidized condition, and improves the tap density of this fluidized-bed.
7. the process of claim 1 wherein that this fluidizing medium comprises propylene gas and at least a other gas, the method comprises fluidized-bed is remained on turbulence state at least, reduces the partial pressure of propylene of fluidizing medium, and improves the tap density of fluidized-bed.
8. the method for any one in claim 1～3 and 6～7, it comprises operating air density from being reduced to lower than critical gas density higher than critical gas density, and improves the tap density of fluidized-bed.
9. the method for any one in claim 1～3 and 6～7, it comprises catalyst composition is incorporated in described reactor, and to form APS be that 0.356mm (0.014 inch) is to the fluidized-bed of 3.048mm (0.12 inch).
10. the method for any one in claim 1～3 and 6～7, it comprises that making SBD is 240.28kg/m 3(15lb/ft 3)～560.65kg/m 3(35lb/ft 3) polymer beads.
11. the method for any one in claim 1～3 and 6～7, it comprises makes fluidizing medium pass through reactor with the speed of 0.24m/ second (0.8ft/ second)～1.52m/ second (5.0ft/ second).
12. the method for any one in claim 1～3 and 6～7, it comprises that the tap density with fluidized-bed improves 10wt% to 100wt%.
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